Catalytic alkylation process



4Patented Nov. 2o, 1945 William E. Ross, Berkeley, Sumner H. McAllister, Lafayette, and John Anderson, Berkeley, Calif., assignors to Shell Development Company, San Fi-anclsco,- Calif., a corporation ci Delaware No Drawing. Application February 27, 194i., Serial No. 380,892

11 claims. tcl.' 26o-scar) This invention relates to the alkylation of organic compounds by reaction with suitable alkylating agents, including aralkylating agents and the like in the presence of catalysts of the Friedel-Crafts type. It deals particularly with the use of more advantageous catalyst mixtures in such reactions.

Alkylations oi a wide variety of compounds, using a great many dillerent alkylating agents' have been carried out in the laboratory with aluminum chloride and related catalysts. These reactions have been severely restricted in their commercial applications, however, because of the diillcultles encountered in the attemptsjo employ catalysts of this type in large scale alkylation operations. This is especially the case in alkylating aromatic and aliphatic hydrocarbons with olens. Therefore, for the purpose oi making the invention more clear, it will be described with more particular reference to its application to such alkylations. It will be understood, however, that the invention is not limited to these illustrative applications, but may be applied with equal advantage to the alkylation of other organic compounds .having a hydrogen atom which can be substituted by alkyl or aralkyl groups, which may or may not substituted, using the-same or other agents capable of introducing such groups.

Aluminum chloride is a rather volatile highmelting solid which is relatively insoluble yin the y aromatic and aliphatic hydrocarbon to be alkylated and it is most dliilcult vto secure eicient contact of alkylating agent, hydrocarbon and aluminum chloride Without the application of excessive quantities oi the latter. Furthermore, aluminum chloride and related alkylation catalysts of the Friedel-Crafts type react readily with traces of moisture and/or impurities in the reactants'particularly' the olefin and/or traces of products of side reactionsto form sticky sludge-like material. These sludge-like materials `are substantially insoluble in alkylationreaction mix- .'tures. They 'coat the particles oi aluminum chloride and prevent proper contact of the catalyst with the allrylating agent and compound being allzylated. This difiiculty is further aggravated by the fact that once the catalyst particles become coated with, this sludgey they tend to agglomerate into hard, sticky lumps. This seriously interferes with continuous methods of carrying out alkylations with these catalysts. Thus, for exam-` ple, if it is attempted to continuously pass a. slurry of aluminum chloride and isoparaln and alkylating agent through a tubular reactor, it is dll' dit

found that the reactor invariably becomes quickly coated and choked with this sludge-like mal terial. As a result, alkylations carried out with these catalysts require excessive amounts of aluminum chloride and the larger proportion ci the catalyst is discarded as practically worthless sludge. Furthermore, the alkylation must be carried out batch-wise or intermittently. In the production'of ne chemicals where the cost oi' the catalyst is usually a small fraction oi the total cost and operations are carried out ln small batches,r this lnefilcient utilization ol the catalyst may be of relatively little importance. But in the production of motor fuels by alkylating aromatic and/or tertiary carbon atom-containing aliphatic hydrocarbons with olens or the like where large-scale operations with inexpensive starting materials are necessary for ncial success, the cost oi the catalyst must be lsept at a minimum. In alkylations of this type, more over, the prevention of sludge formation and its attendant complications are especially cult due to presence in the starting material of m purities which promote sludge formation with aluminum chloride and like catalysts.

An important object of the present invention is to provide an allrylation process in which sludge formation is mid. Another object or the invention is to reduce the consumption of catalyst involved in Friedel-Crafts type oi alkylations. A further object is to provide a more economical liquid phase method ci carrying out alkylations in the presence o aluminum chloride and the lilre. .Additional objects and advantages ol the process or the invention will be apparent from the following description.

llt has been proposed to employ as allrylatlon catalysts,I complex Aaddition commands of the Gustavson and Ansolvo-acid types in which aluminum vchloride or bromide is bound by sec ondary valence bonds to one or more organic compounds. These addition compounds are riormally liquid and are in certain respects superior to the use of aluminum chloride or bromide alone. Under alkylation conditions, however, the organic components or the complex tend to split oit and be substituted by the compound being allrylated and/or to be alkylated by the alkylating arent used. As a result, the composition of the catan lyst is diiiicult to maintain constant and its viseosity tends to change with use so that constant careful supervision is' required in order to keep proper proportions in the reaction mixture. Furthermorathese side reactions not only reduce the yield ot. desired product, but also in-.

troduce unwanted impurities. To overcome these disadvantages it has been suggested that complex double salts of aluminum chloride and aluminum bromide such as are produced by reactl ing these aluminum halides with alkali metal,

they are liquid the equilibrium between the reactants and the alkylation product is unfavorable andlthe conversions impractically low. It is usual, therefore, to use these catalysts impregnated on porous carriers. In alkylation reactions,

,such solid catalystsl are rapidly coated with reaction products or sludge andsoon lose their ability to catalyze the desired alkylation even when frequently subjected to regeneration treatments which of course add to the expense of the process.

In accordance with the present invention, many of the disadvantages of former alkylationprocesses are avoided by substituting for the aluminum halide alkylating agents used therein, a liquid alkylation catalyst comprising a complex double compound of an anhydrous aluminum halide and a hydrogen halide and a metal' salt which does not react with the aluminum halide. Catalysts of this type are described and claimed in our'copending application, Serial No. 363,676, filed October 31,'1940, Patent No. 2,370,195, of which the present application is a continuation-impart.

From an economic standpoint there are advantages in using liquid mixtures comprising the double compound of anhydrous aluminum cholride and hydrogen -chloride. Aluminum chloride is preferred not only because of its availability at a reasonable price, but also because a wider variety of metal salts form therewith, mixtures which. are liquid at favorable alkylation temperatures. By employing with the chosen aluminum halide, onlymetal salts, in which term it is intended to include double salts and mixtures of metal salts, which do not react therewith, the secondary valence forces of the aluminum halide are preserved for the formation of the desired complex, i. e., hydrogen aluminum halide. As a result, a very active alkylation catalyst is obtained.

The non-reactive metal salt which it will be most desirable to use in a given alkylation will depend upon the temperature which is best suited to the reaction. From the melting point-composition diagram of binary mixtures of the salt .and the chosen aluminum halide, the temperature range in which the catalyst will be liquidcan be ascertained. Such diagrams have been determined for mixtures oi? the more common metal salts with aluminum-chloride and aluminum bromide and, therefore, it is also known which metals react with the aluminum halides and which do not. Thus, such salts as the halides of sodium, potassium, lithium, ammonium, calcium, magnesium, barium, copper, silver. etc., are known to form stable double salts with the corresponding aluminum halides and these binary mixturesare thus unsuitable for use in the present process. In other cases, such as the sulfates, nitrates, phosphates and other applicable metal salts of the stronger acids and in the case of binary, ternary and quaternary mixtures of metal salts, it is a simple matter to determine their suitability. Since the metal salts employed do not react with the aluminum halide used their mixture therewith will form simple eutectics or mixed crystals which are easily identified. Antimony trichloride is a preferred metal salt to use with aluminum chloride. Antimony tribromide, on the other hand, cannot be employed per se with aluminum bromide because it forms a double salt of the formula AlBra.SbBra therewith. As examples 0f metal salts which may -be used in the alkylation A ature, the catalysts prepared with certain metal salts are more advantageous alkylation catalysts than those produced from other salts. Thus, for example, catalysts prepared from metal salts having normal boiling points below about 300 C. are preferred because not only do they generally permit lower alkylation temperatures to be used but also they form catalysts which are easily recovered and reactivated by a lsimple distillation treatment. Also, it is preferred to choose metal salts or mixtures which have a relatively low solubility in the organic components of the alkylation mixture since this reduces the cost of recovery oi salt from the product. Metal saltswhich undergo reaction with the alkylatingr agent or compound to be alkylated, as for example, halides which act as halogenating agents under the conditions of alkylation used are preferably not employed. For this reason, the applicable halides gtererally contain the metal in a lower valent s a e. Y

l It is desirable that the aluminum halide comprise at least 3 mol oi the catalyst mixture in order that a practical alkylation rate may be maintained. Preferably a molar excess oi' metal salt over aluminum halide is used in order to -suppress undesirable side reactions and more preferably two or more mols of metal salt or mixture oi metal salts are used per mol of free aluminum halide. In general, it is advantageous to employ mixtures corresponding to or approaching the eutectic mixture as lower alkylation temperatures may thus be used. However, Where the eutectic composition does not contain suillcient free aluminum halide to provide the desired alkylation rate or contains excessive amounts which produce undesirable side reactions, the composition may be adjusted to obtain a catalyst of more favorable alkylating activity and a slightly higher melting point. Thus, for example, excellent alkylation catalysts have been prepared from mixtures comprising 76 to 97 mol antimony trichloride and 24 to 3 mol aluminum chloride. Those prepared from mixtures containing about 9 mol of free aluminum chloride and melting at about 70 C. are espectially advantageous. Mixtures containing higher proportions of aluminum chloride to antimony trichloride may, however, be used, in which case the melting point of the catalyst is somewhat increased.

The chosen mixture of aluminum halide and non-reactive metal salt may be treated with a hydrogen halide prior to use or the aluminum halide-hydrogen halide complex may be formed in the catalyst during the alkylation reaction by supplying the hydrogen halide with the reactants. Instead of using hydrogen halide itself, a material which will form hydrogen halide under the conditions may be employed. Thus. foi-example, chlorine, bromlne. or organic halides or a small amount of water may be used. When alkyl halides are used asalkylation agents, no other hydrogen halide source may .be required.

Generally, it is preferable to use the hydrogen halide corresponding to the aluminum halide em.

ployed. A concentration of hydorgen halide in the feed of about 0.01 to about 1% is usually sufficient to maintain the desired activity of the catalyst, but higher concentrations up to or more may be used, although these usually require recovery of the excess.

An advantage of the present process is that a substantial amount of hydrogen halide may be taken `up in the metal salt mixture'bysolution,

thus tending to increase the effective partial under the same reaction conditions` found suitable with the usual aluminum halide catalysts. Thus, for example, more drastic conditions are generally desirable when normal parafilns are to pressure of hydrogen halide in contact with the aluminum halide with reduced'danger of contamination of the product by any excess halide.

used. Such contamination is especially undesirable in the .production of motor fuels -by alkylation since small amounts of chlorides tend to reduce the response of the fuels `to addition to lead tetraethyl.

, Any apparatus suitable for contacting the reactants with the liquid catalyst may be used. A form of apparatus which is preferred when reactants in the liquid phase are to be employed is described in U. S. Patent 2,232,674. Alternatively, the compound to be alkylated and the alkylating agent either or both in either the liquid or gaseous phase, may be bubbled through a preferably mechanically agitated body of the liquid aluminum halide-metal salt mixture. Jets or other means of injecting the reactants may provide the desired agitation. Towers, provided with trays or perforated plates or packing material over which the catalyst mixture is allowed to flow, may also be used. -In some cases it may be desirable to have counter-current flow between a mixture of the compound being alkylated in the liquid `phase and the catalyst mixture on the one hand and the alkylating agent, for example an olefin, in the gaseous state and hydrogen halide on the other. Batch or intermittent methods of operation may be employed although the process has special advantage in continuous operation. a

For the .preparation of mono-alkyl derivatives,

` found advantageous. While in most cases tem- $0 is of special importance.

be reacted than when alkylating aromatic hydrocarbons or tertiary carbon atom-containing aliphatic hydrocarbons. As a rule a high proportion of catalyst phase to liquid hydrocarbons is desirable for promoting high yields of gasoline and volume ratios of about 0.1 to 1.2 have been perature-and time of alkylation are, within limits. compensating factors, it has been found; in the case of the alkylation of aromatic hydrocarbons and phenols, that the time of reaction after the addition of alkylating agent has been stopped, Thus, in such cases, the proportion of mono-alkylated products can be materially increased, with a corresponding decrease' in the amount of unalkylated aromatic compound in the product, by providing time for 85 continued reaction out of contact with newly added alkylating agent, particularly olefin.

Other suitable variations in the process may be made. a

Typical of the advantages of the process of 40 the invention are the results in alkylating isoit is desirable to employ at least a small molecular y excess of the. compound being alkylated compared with the alkylating agent used. WhereY isoparatiins are being alkylated with olens it is advantageous to use a substantial excess of the isoparaiiln, preferably. at least two mols of isoparailin permol of'olenn. Most preferably a feed containing a stoichiometric excess of the compound to be alkylated, based on the alkylating agent used, is introduced'into a circulating mass of reacted mixture containing the liquid catalyst salt mixture dispersed therewith whereby the reaction is effected in the presence of a higher ratio of compound to be alkylated to alkylating agent than is present in the feed. In this way the alkylation of isoparaillns with oleilns, for example, may economically be carried out at lsoparafiln to olefin ratios of the order of 50 to v100 to l or more.

The process is carried out at temperatures at which the catalyst mixtures used are in the liquid state and preferably not more than about 25 C. above the melting point of the chosen catalyst butane with ethylene. For this alkylation, a mixturel of aluminum chloride and antimony trichlorlde in the proportions of 7.5 to 92.5 parts by Weight were used. A steel reactor provided with a stirrer and heating coil was charged with this catalyst and isobutane in the proportions of 489 partsto 377 parts by weight together with sufficient water to produce the necessary amount of hydrogen chloride in the catalyst. The mixture was heated, the stirrer started and ethylene was then slowly added under sufficient .pressure to maintain all the hydrocarbon` in the reactor in the liquid'phase. The ethylene apparently reacted almost .instantaneously as the pressure never appreciably exceeded that of isobutane at the temperature of operation which was C. Over a period of y11/2 hours, 66 parts by weight/of ethylene were added. On completion of the frun the catalyst and hydrocarbon phases were separated and the products boiling higherthan isobutane were recovered and analyzed. These were found to correspond to a yield of 292% based on the ethylene used or of the theoretical dimethyl butane yield. This product was completely saturated and 95% boiled `be1owj1'10 C. Little or no chlorine was found in the product. This type of product has an octane rating of about 87. l

The pounds of product Qbtained per pound of aluminum chloride were'more than twice that obtained under the best conditions with avsolid aluminum chloride catalyst. Furthermore, by flash distillation of the used catalyst which solidified after the run.. ,92% wasrecovered vas a mixture. Thus. in general. temperatures belOW u' straw-colored distillate which couldbe reusedrepeatedly by merely adjusting the aluminum chloride-antimony trichloride ratio.

Similai` good results may be obtained in alkytane, methyl cyclohexane and like tertiary carbon atoms containing aliphatic hydrocarbons or the corresponding unbranched hydrocarbons or suitable substitution products thereof, using ethylene or higher oleilns such as propylene, normal or isobutylenes, one or more amylenes or higher olefins or oleiln mixtures or oleiln polymers. Instead ot the oleilns the corresponding alkyl halides or alkyl sulfates or primary alkyl halides or suliates may be used.l Other esters such as phosin this specification and the appended claims.

Thus, for example,'benzyl chloride or either of the chloroethyl benzenes may be reacted with benzene in the presence of liquid mixtures of aluminum chloride and antimony chloride using operating conditions analogous to those described for the reaction of is'obutane and ethylene.

It will thus be apparent that the invention is capable of wide modification not only with respect to the alkylationswhich may be carried out, but also in regard to the operating procedures which may be used.

We claim as our invention:

1. In 'a process for 'producing gasoline motor fuel from normally gaseous hydrocarbons, the step of reacting isobutane with a normally gaseous oleiln in the presence of an alkylation catalyst comprising a liquid mixture of a complex double compound of anhydrous aluminumchloride and a hydrogen halide and a molecular excess based upon said aluminum chloride of a metal salt which does not react with the aluminum chloride.

2. In a process for producing gasoline motor fuel from a normally gaseous olelln, the step of treating a liquid mixture comprising said oleiln and a stoichiometric excess of isoparaihn with a liquid mixture of a complex double compound of anhydrous aluminum chloride and a. hydrogen halide and a metal salt which does not react with aluminum chloride at an alkylation temperature 3. In a process for producing gasoline vmotor fuel by alkylating a hydrocarbon inwhich a. hydrogen atom can be substituted by an alkyl group, the improvement which comprises reacting said hydrocarbon with an olen in the presence of a liquid mixture of a complex double compound of anhydrous aluminum chloride and a hydrogen halide and a metal salt which does not react with aluminum chloride at an alkylation temperature below 200 C.

4.In a process for producing gasoline motor fuel from a hydrocarbon mixture containing an lating isopentaneLisohexane, methyl cyclopenolefin and an isoparamn by treatment with an aluminum chloride catalyst under alkylating conditions.' the improvement which comprises eifectlation in the presence of a molten mixture of an aluminum halide, the corresponding hydrogeny halideand a metal salt which does not react with said aluminum halideand which has a normal boiling point below 300 C.

6. In a process of alkylating an aromatic compound by reaction with an alkylating agent, the improvement which comprises eifecting said a1- kylation in the presence of a molten mixture of an aluminum halide, the corresponding hydrogen halide and a metal salt which does not react with said aluminum halide under the alkylating conditions.

'1. In a process of alkylating an organic compound in which a hydrogen atom can be substi- ,tuted by an alkyl group by reaction with an alkylating agent, the improvement which comprises contacting said reactants in the presence of a liquid mixture of an aluminum halide, a hydrogen halide and a metal salt which does not react with said aluminum halide.

8. In a process of alkylating an organic compound in which a hydrogen atom can be substituted by an alkyl group by reaction with an alkylating agent, the improvement which comprises contacting said reactants in the presence of a liquid mixture of aluminum chloride. a hydrogen en halide and a molecular excess based upon said aluminum chloride of antimony trichloride.

9. In a process of alkylating an organic com-. pound in which a hydrogen Vatom can be substituted by an alkyl group by reaction with an alkylating agent, the improvement which comprises contacting a mixture of said reactants and a hydrogen halide with a liquid mixture of aluminum chloride and antimony trichloride.

10. In a process of alkylating an organic compound in which a hydrogen atom can be substituted by an alkyl group by reaction with an alkylating agent, the improvementI which comprises contacting said reactants with a liquid mixture of aluminum chloride and antimony trichloride in the presence of a hydrogen halide.

11. In a process of alkylating an organic compound in which a hydrogen atom can be substituted by an alkyl group by reaction with an alkylating agent, the improvement which comprises contacting said reactants in the presence of a liquid mixture of an aluminum halide and a molecular excess based upon said aluminum halide of a metal salt which does not react with said aluminum halide in the presence of a hydrogen halide.

WILLIAM E. Ross. sUMNnR H. Mcms'rna. JOHNv ANDERSON. 

